A large variety of materials have been synthesized and evaluated as cathode materials for Li-batteries. Notable among them is the layered LiMO2 (M=Co, Ni, Mn) compositions which have already found application in rechargeable lithium ion battery technology. However, only about 50-60% of the theoretical capacity can be utilized in practical cells because of structural and chemical instabilities associated with deep charge of Li1−xMO2(x>0.5) along with safety issues. In order to increase the energy density, recent developments have focused on the lithium rich Li—Ni—Mn—Co oxide compounds that have significantly higher capacities. See for example Thackeray et al U.S. Pat. No. 7,135,252 and US 2006/0099508, the disclosures of which are incorporated by reference. These materials can be represented using either (i) structurally integrated two-component solid solution notations such as xLi2MnO3(1−x)LiMO2 (layered-layered in which the Li2MnO3 component is electrochemically activated above 4.4 V vs. Li/Li+) or (ii) standard notation as Li1+yM1−yO2 (M=Mn, Ni, Co). For example, the composition 0.6Li[Li1/3Mn2/3]O2-0.4Li[Mn0.3Ni0.45Co0.25]O2 (hereafter Li-rich MNC) can be alternately expressed as Li1.2Mn0.525Ni0.175Co0.1O2 in the standard notation for such layered compositions. Electrodes based on these Li-rich MNC compositions can operate at high anodic potentials of 4.9 V vs. Li/Li+ and provide capacities >250 mAh g−1. There are still major issues that need to be addressed before these lithium rich compounds can be considered as high-energy cathodes for production Li-ion batteries, especially for electric vehicle applications. Notable among these are poor rate capability, high first cycle irreversibility and significant decrease in the discharge voltage plateau with successive cycling. The large irreversible capacity loss in the range of 50-100 mAh g−1 in the first cycle is attributed to the extraction of Li2O followed by elimination of oxygen ion vacancies from the lattice during first charge, resulting in a lower number of sites for insertion and extraction of Li+ in the subsequent cycles. Further, detailed structural and phase transitions associated with such lithiation-delithiation processes at higher voltage (>4.4 V) are not fully understood yet.